EP2867166B1 - Metallophosphat-molekularsiebe, verfahren zur herstellung und verwendung - Google Patents

Metallophosphat-molekularsiebe, verfahren zur herstellung und verwendung Download PDF

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EP2867166B1
EP2867166B1 EP13808484.3A EP13808484A EP2867166B1 EP 2867166 B1 EP2867166 B1 EP 2867166B1 EP 13808484 A EP13808484 A EP 13808484A EP 2867166 B1 EP2867166 B1 EP 2867166B1
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mole ratio
varies
group
value
alpo
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EP2867166A1 (de
EP2867166A4 (de
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Gregory J. Lewis
Lisa M. Knight
Paulina Jakubczak
Justin E. STANCZYK
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Honeywell UOP LLC
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UOP LLC
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Priority claimed from US13/537,411 external-priority patent/US8871177B2/en
Priority claimed from US13/537,448 external-priority patent/US8911614B2/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/54—Phosphates, e.g. APO or SAPO compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/83—Aluminophosphates [APO compounds]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/065—Aluminophosphates containing other elements, e.g. metals, boron the other elements being metals only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/38—Base treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/40—Special temperature treatment, i.e. other than just for template removal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • This invention relates to a new family of charged metallophosphate-based molecular sieves designated AlPO-59. They are represented by the empirical formula of: R + r M m 2+ EP x Si y O z where M is a divalent framework metal such as magnesium or zinc, R is an organoammonium cation such as ethyltrimethylammonium and E is a trivalent framework element such as aluminum or gallium.
  • Zeolites are crystalline aluminosilicate compositions which are microporous and which are formed from corner sharing AlO 2 - and SiO 2 tetrahedra. Numerous zeolites, both naturally occurring and synthetically prepared are used in various industrial processes. Synthetic zeolites are prepared via hydrothermal synthesis employing suitable sources of Si, Al and structure directing agents such as alkali metals, alkaline earth metals, amines, or organoammonium cations. The structure directing agents reside in the pores of the zeolite and are largely responsible for the particular structure that is ultimately formed. These species balance the framework charge associated with aluminum and can also serve as space fillers.
  • Zeolites are characterized by having pore openings of uniform dimensions, having a significant ion exchange capacity, and being capable of reversibly desorbing an adsorbed phase which is dispersed throughout the internal voids of the crystal without significantly displacing any atoms which make up the permanent zeolite crystal structure. Zeolites can be used as catalysts for hydrocarbon conversion reactions, which can take place on outside surfaces of the zeolite as well as on internal surfaces within the pores of the zeolite.
  • Wilson et al. developed aluminophosphate molecular sieves, the so-called AlPOs, which are microporous materials that have many of the same properties of zeolites, but are silica free, composed of AlO 2 - and PO 2 + tetrahedra (See US 4310440 ) . Subsequently, charge was introduced to the neutral aluminophosphate frameworks via the substitution of SiO 2 tetrahedra for PO 2 + tetrahedra to produce the SAPO molecular sieves (See US 4440871 ).
  • Another way to introduce framework charge to neutral aluminophosphates is to substitute [M 2+ O 2 ] 2- tetrahedra for AlO 2 - tetrahedra, which yield the MeAPO molecular sieves (see US 4567029 ) . It is furthermore possible to introduce framework charge on AlPO-based molecular sieves via the introduction both of SiO 2 and [M 2+ O 2 ] 2- tetrahedra to the framework, giving MeAPSO molecular sieves (See US 49973785 and EP 161489 B1 ).
  • Applicants have synthesized a new family of charged metallophosphate framework materials that contain a +3 valence metal, such as aluminum or gallium, and additionally at least one of a +2 valence metal (such as magnesium or zinc) and silicon, designated AlPO-59.
  • a +3 valence metal such as aluminum or gallium
  • a +2 valence metal such as magnesium or zinc
  • silicon designated AlPO-59.
  • the +3 valence metal is Al
  • the AlPO-59 materials have a unique topology that falls in the class of structures known as ABC-6 nets (See American Mineralogist, 66, 777-788 (1981 )).
  • the microporous AlPO-59 materials can be prepared with the ethyltrimethylammonium (ETMA) structure directing agent.
  • ETMA ethyltrimethylammonium
  • microporous crystalline metallophosphate material according to claim 1.
  • one embodiment of the invention is a microporous crystalline material having a three-dimensional framework of at least EO 2 - and PO 2 + tetrahedral units and furthermore, at least one of [M 2+ O 2 ] 2- and SiO 2 tetrahedral units and an empirical composition in the as synthesized form and anhydrous basis expressed by an empirical formula of: R + r M m 2+ EP x Si y O z where M is at least one metal cation of valence +2 selected from the group consisting of Be 2+ , Mg 2+ , Zn 2+ , Co 2+ , Mn 2+ , Fe 2+ , Ni 2+ , "m" is the mole ratio of M to E and varies from 0 to 1.0, R is the organoammonium cation ethyltrimethylammonium (ETMA +
  • Another embodiment of the invention is a process for preparing the crystalline microporous metallophosphate molecular sieve described above.
  • the process comprises forming a reaction mixture containing reactive sources of R, E, P, one or both of M and Si, and heating the reaction mixture at a temperature of 60°C to 200°C for a time sufficient to form the molecular sieve, the reaction mixture having a composition expressed in terms of mole ratios of the oxides of: aR 2 O : bMO : E 2 O 3 : cP 2 O 5 : dSiO 2 : eH 2 O where "a” has a value of 0.75 to 16, "b” has a value of 0 to 2, “c” has a value of 0.8 to 8, "d” has a value of 0 to 4, and "e” has a value from 30 to 800.
  • Yet another embodiment of the invention is a hydrocarbon conversion process using the above-described molecular sieve as a catalyst.
  • the process comprises contacting at least one hydrocarbon with the molecular sieve at conversion conditions to generate at least one converted hydrocarbon.
  • Still another embodiment of the invention is a separation process using the crystalline AlPO-59 material.
  • the process may involve separating mixtures of molecular species or removing contaminants by contacting a fluid with the AlPO-59 molecular sieve. Separation of molecular species can be based either on the molecular size (kinetic diameter) or on the degree of polarity of the molecular species. Removing contaminants may be by ion exchange with the molecular sieve.
  • the instant microporous crystalline material (AlPO-59) has an empirical composition in the as-synthesized form and on an anhydrous basis expressed by the empirical formula: R + r M m 2+ EP x Si y O z
  • M is at least one framework divalent cation and is selected from the group consisting of alkaline earth and transition metals.
  • M cations include but are not limited to beryllium, magnesium, cobalt (II), manganese, zinc, iron(II), nickel and mixtures thereof.
  • R is the organoammonium cation ethyltrimethylammonium (ETMA + ), and "r" is the mole ratio of R to E and varies from 0.1 to 2.0.
  • m is the mole ratio of M to E and varies from 0 to 1.0
  • x is mole ratio of P to E and varies from 0.5 to 2.0
  • the ratio of silicon to E is represented by "y” which varies from 0 to 1.0 and "m” + “y” ⁇ 0.1.
  • E is a trivalent element which is tetrahedrally coordinated, is present in the framework and is selected from the group consisting of aluminum, gallium, iron(III) and boron.
  • the microporous crystalline metallophosphate AlPO-59 is prepared by a hydrothermal crystallization of a reaction mixture prepared by combining reactive sources of R, E, phosphorous, and one or both of M and silicon.
  • a preferred form of the AlPO-59 materials is when E is Al.
  • the sources of aluminum include but are not limited to aluminum alkoxides, precipitated aluminas, aluminum metal, aluminum hydroxide, aluminum salts and alumina sols.
  • Specific examples of aluminum alkoxides include, but are not limited to aluminum ortho sec-butoxide and aluminum ortho isopropoxide.
  • Sources of the other E elements include but are not limited to organoammonium borates, boric acid, precipitated gallium oxyhydroxide, gallium sulfate, ferric sulfate, and ferric chloride.
  • Sources of phosphorus include, but are not limited to, orthophosphoric acid, phosphorus pentoxide, and ammonium dihydrogen phosphate.
  • Sources of silica include but are not limited to tetraethylorthosilicate, colloidal silica, and precipitated silica.
  • Sources of the M metals include the halide salts, nitrate salts, acetate salts, and sulfate salts of the respective alkaline earth and transition metals.
  • R is the organoammonium cation ETMA + and the sources include the hydroxide, chloride, bromide, iodide and fluoride compounds. Specific examples include without limitation ethyltrimethylammonium hydroxide, ethyltrimethylammonium chloride. In particular R is ETMA + .
  • the reaction mixture containing reactive sources of the desired components can be described in terms of molar ratios of the oxides by the formula: aR 2 O : bMO : E 2 O 3 : cP 2 O 5 : dSiO 2 : eH 2 O where "a” varies from 0.75 to 16, "b” varies from 0 to 2, “c” varies from 0.8 to 8, “d” varies from 0 to 4, and "e' varies from 30 to 800. If alkoxides are used, it is preferred to include a distillation or evaporative step to remove the alcohol hydrolysis products.
  • the reaction mixture is now reacted at a temperature of 60°C to 200°C and preferably from 125°C to 175°C for a period of 1 day to 3 weeks and preferably for a time of 2 days to 10 days in a sealed reaction vessel at autogenous pressure.
  • the solid product is isolated from the heterogeneous mixture by means such as filtration or centrifugation, and then washed with deionized water and dried in air at ambient temperature up to 100°C.
  • AlPO-59 seeds can optionally be added to the reaction mixture in order to accelerate the formation of the desired microporous composition.
  • the AlPO-59 aluminophosphate-based material which is obtained from the above-described process, is characterized by the x-ray diffraction pattern, having at least the d-spacings and relative intensities set forth in Table A below.
  • the AlPO-59 is thermally stable up to a temperature of at least 400°C, and in another embodiment the AlPO-59 is thermally stable up to a temperature of at least 500°C.
  • the AlPO-59 may be modified in many ways to tailor it for use in a particular application. Modifications include calcination, ammonia calcinations, ion-exchange, steaming, various acid extractions, ammonium hexafluorosilicate treatment, or any combination thereof, as outlined for the case of UZM-4 in US 6,776,975 B1 . Properties that are modified include porosity, adsorption, framework composition, acidity, thermal stability, etc.
  • the AlPO-59 material will contain some of the exchangeable or charge balancing cations in its pores. These exchangeable cations can be exchanged for other cations, or in the case of organic cations, they can be removed by heating under controlled conditions.
  • a preferred method of removing organic cations from the pores is ammonia calcination. Calcination in air converts the organic cations in the pores to protons, which can, for example, lead to some removal of Al from the framework upon exposure to water vapor.
  • the organic cation in the pore is replaced by NH 4 + cation and the framework remains intact (See Studies in Surface Science, (2004) vol.
  • Typical conditions for ammonia calcinations include the use of gaseous anhydrous ammonia flowing at a rate of 1.1 l/min while ramping the sample at 5°C/min to 500°C and holding at that temperature for a time ranging from 5 minutes to an hour.
  • the resulting ammonium form of AlPO-59 has essentially the diffraction pattern of Table A.
  • the ammonium form of AlPO-59 may then be ion-exchanged to any other form, resulting in a material with a modified composition, AlPO-59M, given by the empirical formula: M' n p+ M m 2+ EP x Si y O z
  • M is at least one framework metal cation of valence +2 selected from the group consisting of Be 2+ , Mg 2+ , Zn 2+ , Co 2+ , Mn 2+ , Fe 2+ , Ni 2+
  • M' is selected from the group consisting of NH 4 + , H + , alkali metals, alkaline earth metals, rare earth metals and mixtures thereof
  • n is the mole ratio of M' to E and has a value of 0.03 to 2.0
  • p is the weighted average valence of M'
  • E is a trivalent element selected from the group consisting of aluminum, gallium,
  • AlPO-59 When AlPO-59 is calcined in air, there can be loss of metal from the framework, such as Al, which can alter the x-ray diffraction pattern from that observed for the as-synthesized AlPO-59 (See Studies in Surface Science, (2004) vol. 154, p.1324 - 1331 ). Some AlPO-59 compositions may not be stable to air calcination and subsequent exposure to water. Stability to air calcinations is favored by AlPO-59 compositions containing some Si.
  • the stable air calcined AlPO-59 materials, AlPO-59C are characterized on an anhydrous basis by the empirical formula: H a M m 2+ EP x Si y O z
  • M is at least one metal cation of valence +2 selected from the group consisting of Be 2+ , Mg 2+ , Zn 2+ , Co 2+ , Mn 2+ , Fe 2+ , Ni 2+
  • "m” is the mole ratio of M to E and varies from 0 to 1.0
  • H is a proton
  • "a” is the mole ratio of H to E and has a value of 0.1 to 2.0
  • E is a trivalent element selected from the group consisting of aluminum, gallium, iron, boron and mixtures thereof
  • x is mole ratio of P to E and varies from 0.5 to 2.0
  • y is the mole ratio of Si to E and varies from 0.05 to 1.0
  • "z” is
  • the crystalline AlPO-59 materials of this invention can be used for separating mixtures of molecular species, removing contaminants through ion exchange and catalyzing various hydrocarbon conversion processes. Separation of molecular species can be based either on the molecular size (kinetic diameter) or on the degree of polarity of the molecular species.
  • the AlPO-59 compositions of this invention can also be used as a catalyst or catalyst support in various hydrocarbon conversion processes.
  • Hydrocarbon conversion processes are well known in the art and include cracking, hydrocracking, alkylation of both aromatics and isoparaffin, isomerization, polymerization, reforming, hydrogenation, dehydrogenation, transalkylation, dealkylation, hydration, dehydration, hydrotreating, hydrodenitrogenation, hydrodesulfurization, methanol to olefins, methanation and syngas shift process.
  • Specific reaction conditions and the types of feeds which can be used in these processes are set forth in US 4,310,440 , US 4,440,871 and US 5,126,308 .
  • Preferred hydrocarbon conversion processes are those in which hydrogen is a component such as hydrotreating or hydrofining, hydrogenation, hydrocracking, hydrodenitrogenation, hydrodesulfurization, etc.
  • Hydrocracking conditions typically include a temperature in the range of 400° to 1200°F (204-649°C), preferably between 600° and 950°F (316-510°C).
  • Reaction pressures are in the range of atmospheric to 3,500 psig (24,132 kPa g), preferably between 200 and 3000 psig (1379 - 20,685 kPa g).
  • Contact times usually correspond to liquid hourly space velocities (LHSV) in the range of 0.1 hr -1 to 15 hr -1 , preferably between 0.2 and 3 hr -1 .
  • Hydrogen circulation rates are in the range of 1,000 to 50,000 standard cubic feet (scf) per barrel of charge (178-8,888 std.
  • Suitable hydrotreating conditions are generally within the broad ranges of hydrocracking conditions set out above.
  • reaction zone effluent is normally removed from the catalyst bed, subjected to partial condensation and vapor-liquid separation and then fractionated to recover the various components thereof.
  • the hydrogen, and if desired some or all of the unconverted heavier materials, are recycled to the reactor.
  • a two-stage flow may be employed with the unconverted material being passed into a second reactor.
  • Catalysts of the subject invention may be used in just one stage of such a process or may be used in both reactor stages.
  • Catalytic cracking processes are preferably carried out with the AlPO-59 composition using feedstocks such as gas oils, heavy naphthas, deasphalted crude oil residua, etc. with gasoline being the principal desired product.
  • feedstocks such as gas oils, heavy naphthas, deasphalted crude oil residua, etc.
  • gasoline being the principal desired product.
  • Temperature conditions of 850° to 1100°F, LHSV values of 0.5 to 10 and pressure conditions of from 0 to 50 psig are suitable.
  • Alkylation of aromatics usually involves reacting an aromatic (C 2 to C 12 ), especially benzene, with a monoolefin to produce a linear alkyl substituted aromatic.
  • the process is carried out at an aromatic: olefin (e.g., benzene: olefin) ratio of between 5:1 and 30:1, a LHSV of 0.3 to 6 hr -1 , a temperature of 100° to 250°C and pressures of 200 to 1000 psig.
  • an aromatic: olefin e.g., benzene: olefin
  • Alkylation of isoparaffins with olefins to produce alkylates suitable as motor fuel components is carried out at temperatures of -30° to 40°C, pressures from atmospheric to 6,894 kPa (1,000 psig) and a weight hourly space velocity (WHSV) of 0.1 to 120. Details on paraffin alkylation may be found in US 5,157,196 and US 5,157,197 .
  • the conversion of methanol to olefins is effected by contacting the methanol with the AlPO-59 catalyst at conversion conditions, thereby forming the desired olefins.
  • the methanol can be in the liquid or vapor phase with the vapor phase being preferred.
  • Contacting the methanol with the AlPO-59 catalyst can be done in a continuous mode or a batch mode with a continuous mode being preferred.
  • the amount of time that the methanol is in contact with the AlPO-59 catalyst must be sufficient to convert the methanol to the desired light olefin products.
  • the contact time varies from 0.001 hrs to 1 hr and preferably from 0.01 hr to 1. 0 hr.
  • the Weight Hourly Space Velocity (WHSV) based on methanol can vary from 1 hr -1 to 1000 hr -1 and preferably from 1hr -1 to 100 hr -1 .
  • the process must be carried out at elevated temperatures in order to form light olefins at a fast enough rate.
  • the process should be carried out at a temperature of 300 °C to 600 °C, preferably from 400 °C to 550 °C and most preferably from 450 °C to 525 °C.
  • the process may be carried out over a wide range of pressure including autogenous pressure.
  • the pressure can vary from 0 kPa (0 psig) to 1724 kPa (250 psig) and preferably from 34 kPa (5 psig) to 345 kPa (50 psig).
  • the methanol feedstock may be diluted with an inert diluent in order to more efficiently convert the methanol to olefins.
  • diluents which may be used are helium, argon, nitrogen, carbon monoxide, carbon dioxide, hydrogen, steam, paraffinic hydrocarbons, e. g., methane, aromatic hydrocarbons, e. g., benzene, toluene and mixtures thereof.
  • the amount of diluent used can vary considerably and is usually from 5 to 90 mole percent of the feedstock and preferably from 25 to 75 mole percent.
  • the actual configuration of the reaction zone may be any well known catalyst reaction apparatus known in the art. Thus, a single reaction zone or a number of zones arranged in series or parallel may be used. In such reaction zones the methanol feedstock is flowed through a bed containing the AlPO-59 catalyst. When multiple reaction zones are used, one or more AlPO-59 catalysts may be used in series to produce the desired product mixture. Instead of a fixed bed, a dynamic bed system, e. g., fluidized or moving, may be used. Such a dynamic system would facilitate any regeneration of the AlPO-59 catalyst that may be required. If regeneration is required, the AlPO-59 catalyst can be continuously introduced as a moving bed to a regeneration zone where it can be regenerated by means such as oxidation in an oxygen containing atmosphere to remove carbonaceous materials.
  • a dynamic bed system e. g., fluidized or moving
  • the structure of the AlPO-59 compositions of this invention was determined by x-ray analysis.
  • the x-ray patterns presented in the following examples were obtained using standard x-ray powder diffraction techniques.
  • the radiation source was a high-intensity, x-ray tube operated at 45 kV and 35 mA.
  • the diffraction pattern from the copper K-alpha radiation was obtained by appropriate computer based techniques.
  • Flat compressed powder samples were continuously scanned at 2° to 56° (2 ⁇ ).
  • Interplanar spacings (d) in Angstrom units were obtained from the position of the diffraction peaks expressed as ⁇ where ⁇ is the Bragg angle as observed from digitized data.
  • Intensities were determined from the integrated area of diffraction peaks after subtracting background, "I o " being the intensity of the strongest line or peak, and "I" being the intensity of each of the other peaks.
  • the determination of the parameter 2 ⁇ is subject to both human and mechanical error, which in combination can impose an uncertainty of ⁇ 0.4° on each reported value of 2 ⁇ . This uncertainty is, of course, also manifested in the reported values of the d-spacings, which are calculated from the 2 ⁇ values. This imprecision is general throughout the art and is not sufficient to preclude the differentiation of the present crystalline materials from each other and from the compositions of the prior art.
  • the relative intensities of the d-spacings are indicated by the notations vs, s, m, and w which represent very strong, strong, medium, and weak, respectively.
  • the purity of a synthesized product may be assessed with reference to its x-ray powder diffraction pattern.
  • a sample is stated to be pure, it is intended only that the x-ray pattern of the sample is free of lines attributable to crystalline impurities, not that there are no amorphous materials present.
  • a Teflon beaker was charged with 100.00 g ETMAOH (20 wt. %) and equipped with a high speed stirrer. With stirring, 5.15 g Al(OH) 3 (80.0 wt. %) was added slowly in several portions, allowing time for stirring between additions. The addition took 20 minutes and the reaction mixture was homogenized for an additional 90 minutes, resulting in a solution with a very slight haze. This was followed by the dropwise addition of 14.65 g H 3 PO 4 (85 wt. %), with a pause after every dropperfull was delivered. By the end of the addition, the reaction mixture was a clear solution.
  • Table 1 Representative diffraction lines for the 150°C, 84 hr product are shown in Table 1. Elemental analysis of this product yielded the empirical composition ETMA 0.41 Zn 0.44 AlP 1.44 O 5.75 . Table 1 2- ⁇ d( ⁇ ) I/I 0 % 4.81 18.38 w 7.58 11.65 w 9.00 9.82 w 9.73 9.08 w 12.36 7.16 m 13.18 6.71 m 14.62 6.05 w 16.00 5.54 m 16.52 5.36 w 18.12 4.89 m 19.58 4.53 m 20.20 4.39 w 20.80 4.27 s 21.02 4.22 m 22.46 3.96 m 22.94 3.87 m 23.66 3.76 w 25.02 3.56 w 25.70 3.46 vs 26.54 3.36 m 28.26 3.16 w 29.00 3.08 w 29.38 3.04 w 30.56 2.92 m 31.14 2.87 m 31.94 2.80 m 32.34 2.77 m 33.38 2.68
  • a Teflon beaker was charged with 130.00 g ETMAOH (20 wt. %) and equipped with a high speed stirrer. With stirring, 6.86 g Al(OH) 3 (78.1 wt. %) was added in several portions, forming a nearly clear solution. Then 23.74 g H 3 PO 4 (85 wt. %) was added quickly by the dropperfull, yielding a clear solution. Separately, 3.01 g Zn(OAc) 2 *2H 2 O was dissolved in 15.00 g de-ionized water. This solution was added dropwise with stirring and the reaction mixture remained a clear solution.
  • the reaction mixture was distributed among 7 Teflon-lined autoclaves and digested at temperatures of 95°C for 158 hours and 125, 150, and 175°C for 47 and 158 hours at autogenous pressures.
  • the products were isolated by centrifugation, washed with de-ionized water and dried at room temperature. All of the samples were identified as ZAPO-59 by powder x-ray diffraction.
  • the characteristic diffraction lines for the 95°C sample, which was digested for 158 hours, are shown in Table 2. Elemental analysis of this product yielded the empirical formula ETMA 0.36 Zn 0.41 AlP 1.42 O 5.64 .
  • a Teflon beaker was charged with 130.00 g ETMAOH (20 wt. %) and placed under a high speed stirrer. To this solution 6.86 g Al(OH) 3 (78.1 wt. %) was added in several portions with stirring in between each addition, forming a clear solution. Then 23.74 g H 3 PO 4 (85 wt. %) was added quickly via dropper resulting in a clear solution. Separately, 3.42 g Co(OAc) 2 *4H2O was dissolved in 15.00 g de-ionized water. This solution was added dropwise with stirring, the reaction mixture becoming a purple solution.
  • the reaction mixture was distributed among 7 Teflon-line autoclaves and digested at temperatures of 95°C for 158 hours, and at 125, 150, 175°C for 47 and 158 hours at autogenous pressures.
  • the products were isolated by centrifugation, washed with de-ionized water and dried at room temperature. Other than the 95°C reaction, powder x-ray diffraction showed that the other reactions all gave some CoAPO-59.
  • a pure product was isolated from the 125°C/158 hr reaction. Characteristic diffraction lines for this product are shown below in Table 3. Elemental analysis showed the product to have the empirical formula ETMA 0.31 Co 0.29 AlP 1 . 24 O 5.05 .
  • a Teflon beaker was charged with 130.00 g ETMAOH (20 wt. %) and placed under a high speed stirrer. Then 6.86 g Al(OH) 3 (78.1 wt. %) was weighed out and added in several portions, stirring for a few minutes between additions, yielding a clear solution. This was followed by the addition of 18.99 g H 3 PO 4 (85 wt. %) in a fast dropwise manner. The resulting reaction mixture was slightly hazy. Separately, 2.94 g Mg(OAc) 2 *4H 2 O was dissolved in 15.00 g de-ionized water. This solution was added slowly, dropwise, to the reaction mixture with stirring.
  • the reaction mixture was further homogenized after the addition was completed, becoming a nearly clear solution.
  • the reaction mixture was distributed among 7 Teflon-lined autoclaves and digested at 95°C for 156 hours, and 125, 150, and 175°C for 48 and 156 hours at autogenous pressures.
  • the products were isolated by centrifugation, washed with de-ionized water and dried at room temperature.
  • the products from the 125°C/156 hr and 150°C/48 hr were identified as MAPO-59 via powder x-ray diffraction.
  • the characteristic diffraction lines for the 125°C/156 hr product are shown in Table 4 below.
  • a Teflon beaker was charged with 130.00 g ETMAOH (20 wt. %) and placed under a high speed stirrer. To this solution 7.42 g Ludox AS-40 (40 wt. % SiO 2 ) was added and the mixture stirred briefly. The suspension was transferred to a Teflon bottle and was digested at 95°C for 45 minutes to dissolve the silica. The solution was placed back into the Teflon beaker and stirred while cooling. Next, 24.69 g Al(OH) 3 (78.1 wt. %) was added in several portions taking time to homogenize the reaction mixture after each addition. By the end of the additions, the reaction mixture is a white suspension.
  • Table 5 Table 5a Table 5b 2- ⁇ d( ⁇ ) I/I 0 % 2- ⁇ d( ⁇ ) I/I 0 % 7.64 11.56 w 9.08 9.73 m 9.13 9.68 s 9.86 8.97 w 12.46 7.10 m 12.62 7.01 s 13.22 6.69 m 13.32 6.64 vs 14.80 5.98 w 15.03 5.89 m 16.06 5.52 m 16.18 5.47 m 16.64 5.32 w 16.92 5.24 w 18.20 4.87 m 18.38 4.82 m 19.78 4.49 m 20.12 4.41 m 20.82 4.26 m 21.04 4.22 m 21.20 4.19 m 21.58 4.11 m 21.82 4.07 w 22.54 3.94 m 22.82 3.89 m 22.96 3.87 m 24.24 3.67 w* 24.16 3.68 w* 25.12 3.54 w 25.48 3.49 m 25.94 3.43 vs 26.38 3.38 s 26.58 3.35 m
  • a Teflon beaker was charged with 130.00 g ETMAOH (20 wt. %) and placed under a high speed stirrer. To this solution 7.43 g Ludox AS-40 (40 wt. % SiO 2 ) was added and the mixture stirred briefly. The reaction mixture was transferred to a Teflon bottle and digested at 95°C for 45 minutes to dissolve the SiO 2 . The resulting clear solution was transferred back to the beaker and stirred to cool. An 18.25 g portion of Al(OH) 3 (84.5 wt. %) was added a little at a time with time to stir in between additions. A white suspension resulted which was homogenized further for 25 minutes. Next, 28.50 g H 3 PO 4 (85 wt.
  • a Teflon beaker was charged with 130.00 g ETMAOH (20 wt. %) and placed under a high speed stirrer. To this solution 2.97 g Ludox AS-40 (40 wt. % SiO 2 ) was added and stirred briefly. The suspension was transferred to a Teflon bottle and digested at 95°C for an hour to dissolve the silica. The reaction mixture was transferred back to the beaker and stirred to cool. Then commenced the addition of 18.25 g Al(OH) 3 (84.5 wt. %) a little at a time, allowing time for homogenization in between additions. Following the Al(OH) 3 addition, the reaction mixture was homogenized for 30 minutes.
  • the products from the 150°C reactions and the 175°C/93 hr reaction were identified as ZAPSO-59 via powder x-ray diffraction.
  • the characteristic diffraction lines for the 175°C/93 hr product are given in Table 7 below.
  • a Teflon beaker was charged with 130.00 g ETMAOH (20 wt. %) and placed under a high speed stirrer. To this solution 7.43 g Ludox AS-40 (40 wt. % SiO 2 ) was added and the mixture was stirred briefly. The reaction mixture was transferred to a Teflon bottle and digested at 95°C for an hour to dissolve the SiO 2 . The solution was transferred back to the beaker and stirred to cool. Separately aluminum isopropoxide (AIP) (98 wt. %) was ground to a powder. A total of 41.21 g of the powdered AIP was added to the reaction mixture over an hour with vigorous stirring. After an hour of further homogenization, the solution was nearly clear.
  • AIP aluminum isopropoxide
  • a Teflon beaker was charged with 250.00 g ETMAOH (20 wt. %) and placed under a high speed stirrer. Next, 14.28 g Ludox AS-40 (40 wt. % SiO 2 ) was added to the solution, which was stirred briefly, transferred to a Teflon bottle and digested at 95°C for 90 minutes to dissolve the silica. The resulting solution was transferred back to the beaker and stirred to cool. Then 34.87 g Al(OH) 3 (85.07 wt. %) was added in small portions taking time to stir between additions. Once the addition was completed, the reaction mixture was stirred for an additional 90 minutes resulting in a white suspension.
  • a Teflon beaker was charged with 13.00 g ETMAOH (20 wt. %) and placed under a high speed stirrer. A 6.29 g portion of Al(OH) 3 (85.07 wt. %) was added to the solution in several additions with vigorous stirring. This resulted in a cloudy suspension. Then 23.75 g H 3 PO 4 (85 wt. %) was added to the reaction mixture in a dropwise fashion, the reaction mixture maintaining a cloudy appearance. Separately, 2.94 g Mg(OAc) 2 *4H 2 O was dissolved in 10.08 g de-ionized water.
  • a 288.38 g portion of ETMAOH (20 wt. %) was placed into a Teflon bottle equipped with a magnetic stir bar. Then 16.47g of Ludox AS-40 colloidal silica (40 wt. % SiO 2 ) was added to the Teflon bottle. The bottle was sealed, mixed well and transferred to a 100°C oven and digested for 1.5 hours to dissolve the silica. The solution was then transferred to a beaker, placed under a high speed stirrer and 54.47 g alumina (51.3 wt% Al 2 O 3 ) was added. Once the addition was completed, the reaction mixture was homogenized for an additional 40 minutes. While continuing to mix, 63.28 g H 3 PO 4 (85 wt.
  • reaction mixture was homogenized for an additional 70 minutes. The final mixture was a white gel.
  • the reaction mixture was transferred to a 600cc autoclave. While stirring at 200 rpm, the autoclave was ramped to 165°C over a period of 3 hours and held at 165°C for 72 hours. The reaction product was then collected and washed with deionized water by centrifugation. The solid product was then dried at 100°C.
  • the reaction product was identified as SAPO-59 by powder x-ray diffraction. The characteristic diffraction lines for the product are given in Table 11a below. Elemental analysis showed the as-synthesized product to have the empirical formula ETMA 0.29 AlP 0.69 Si 0.28 O 3.93 .
  • Table 11 Table 11a Table 11b 2- ⁇ d( ⁇ ) I/I 0 % 2- ⁇ d( ⁇ ) I/I 0 % 7.53 11.74 w 8.94 9.88 s 9.32 9.48 m 12.34 7.17 m 12.84 6.89 m 13.12 6.74 s 13.56 6.53 vs 14.62 6.05 w 15.20 5.82 w 15.94 5.56 m 16.40 5.40 w 16.55 5.35 w 18.56 4.78 w 18.08 4.90 m 21.26 4.18 m 19.74 4.49 m 21.72 4.09 m 20.74 4.28 vs 23.00 3.86 m 21.12 4.20 m 23.40 3.80 m 21.73 4.09 w 25.74 3.46 w 22.44 3.96 vs 26.62 3.35 m 22.88 3.88 w 27.12 3.29 m 24.99 3.56 w 29.01 3.08 w 25.84 3.45 vs 29.90 2.99 m 26.50 3.36 m 31.68 2.82 m

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Claims (9)

  1. Mikroporöses kristallines Metallophosphat-Material mit der Bezeichnung AlPO-59 mit einem dreidimensionalen Gerüst aus EO2 --Tetraederinheiten und PO2 +-Tetraedereinheiten und mindestens einer von [M2+O2]2-- und SiO2-Tetraedereinheiten und einer durch die folgende Summenformel ausgedrückten empirischen Zusammensetzung in der wie bei der Synthese anfallenden Form und auf wasserfreier Basis:

            RrM2+ mEPxSiyOz

    wobei M für mindestens ein Gerüstkation mit einer Wertigkeit von +2 aus der Gruppe bestehend aus Erdalkali- und Übergangsmetallen steht, "m" für das Molverhältnis von M zu E steht und von 0 bis 1,0 variiert, R für das Organoammoniumkation Ethyltrimethylammonium (ETMA+) steht, "r" für das Molverhältnis von R zu E steht und einen Wert von 0,1 bis 2 hat, E für ein dreiwertiges Element aus der Gruppe bestehend aus Aluminium, Gallium, Eisen, Bor und Mischungen davon steht, "x" für das Molverhältnis von P zu (Al+E) steht und einen Wert von 0,5 bis 2,0 hat, "y" für das Molverhältnis von Si zu E steht und von 0 bis 1,0 variiert, "m" + "y" ≥ 0,1 und "z" für das Molverhältnis von O zu (Al+E) steht und einen durch die folgende Gleichung bestimmten Wert aufweist: z = 2 • m + r + 3 + 5 • x + 4 • y / 2
    Figure imgb0013
     dadurch gekennzeichnet, dass es das Röntgenbeugungsmuster mit mindestens den folgenden d-Abständen und Intensitäten gemäß Tabelle A aufweist: Tabelle A 2Θ d (Å) I/I0 % 7,69-7,48 11,48-11,81 w 9,15-8,88 9,66-9,95 m-vs 12,55-12,25 7,05-7,22 m 13,30-13,07 6,65-6,77 w-s 14,90-14,51 5,94-6,10 w 16,13-15,87 5,49-5,58 m 16,75-16,37 5,29-5,41 w 18,28-18,02 4,85-4,92 m 19,94-19,41 4,45-4,57 w-m 20,88-20,64 4,25-4,30 m-vs 21,34-20,79 4,16-4,27 m 22,67-22,26 3,92-3,99 m-vs 23,08-22,78 3,85-3,90 w-s 25,28-24,78 3,52-3,59 w 26,11-25,43 3,41-3,50 s-vs 26,67-26,35 3,34-3,38 w-m 28,40-27,86 3,14-3,20 w 29,36-28,78 3,04-3,10 w-m 30,92-30,27 2,89-2,95 w-m 31,36-30,92 2,85-2,89 w-m 32,29-31,70 2,77-2,82 m 35,60-35,02 2,52-2,56 w-m 36,50-35,45 2,46-2,53 w 42,40-41,58 2,13-2,17 w-m 43,69-42,61 2,07-2,12 w 49,21-48,65 1,85-1,87 w 50,98-59,79 1,79-1,83 w-m 55,30-54,23 1,66-1,69 w-m
  2. Metallophosphat-Material nach Anspruch 1, wobei M aus der Gruppe bestehend aus Beryllium, Magnesium, Zink, Cobalt, Mangan, Eisen (II), Nickel und Mischungen davon ausgewählt ist und wobei E für Aluminium steht.
  3. Metallophosphat-Material nach Anspruch 1, wobei "y" und/oder "m" für null stehen oder wobei "m" und "y" jeweils >0 sind und "m" + "y" ≥ 0,2.
  4. Verfahren zur Herstellung eines mikroporösen kristallinen Metallophosphats mit einem dreidimensionalen Gerüst aus EO2 --Tetraedereinheiten, PO2 +-Tetraedereinheiten und mindestens einer von [M2+O2]2--und SiO2-Tetraedereinheiten und einer Zusammensetzung in der wie bei der Synthese anfallenden Form und auf wasserfreier Basis, ausgedrückt durch die folgende Summenformel:

            RrMm 2+EPxSiyOz

    wobei M für mindestens ein Gerüstkation mit einer Wertigkeit von 2+ aus der Gruppe bestehend aus Erdalkali- und Übergangsmetallen steht, "m" für das Molverhältnis von M zu E steht und von 0 bis 1,0 variiert, R für das Organoammoniumkation Ethyltrimethylammonium (ETMA+) steht, "r" für das Molverhältnis von R zu E steht und einen Wert von 0,1 bis 2 hat, E für ein dreiwertiges Element aus der Gruppe bestehend aus Aluminium, Gallium, Eisen (III), Bor und Mischungen davon steht, "x" für das Molverhältnis von P zu E steht und von 0,5 bis 2,0 variiert, "y" für das Molverhältnis von Si zu E steht und von 0 bis 1,0 variiert, "m" + "y" ≥ 0,1 und "z" für das Molverhältnis von O zu E steht und einen durch die folgende Gleichung bestimmten Wert aufweist: z = 2 • m + r + 3 + 5 • x + 4 • y / 2
    Figure imgb0014
     dadurch gekennzeichnet, dass es das Röntgenbeugungsmuster mit mindestens den folgenden d-Abständen und Intensitäten gemäß Tabelle A aufweist: Tabelle A 2Θ d (Å) I/I0 % 7,69-7,48 11,48-11,81 w 9,15-8,88 9,66-9,95 m-vs 12,55-12,25 7,05-7,22 m 13,30-13,07 6,65-6,77 w-s 14,90-14,51 5,94-6,10 w 16,13-15,87 5,49-5,58 m 16,75-16,37 5,29-5,41 w 18,28-18,02 4,85-4,92 m 19,94-19,41 4,45-4,57 w-m 20,88-20,64 4,25-4,30 m-vs 21,34-20,79 4,16-4,27 m 22,67-22,26 3,92-3,99 m-vs 23,08-22,78 3,85-3,90 w-s 25,28-24,78 3,52-3,59 w 26,11-25,43 3,41-3,50 s-vs 26,67-26,35 3,34-3,38 w-m 28,40-27,86 3,14-3,20 w 29,36-28,78 3,04-3,10 w-m 30,92-30,27 2,89-2,95 w-m 31,36-30,92 2,85-2,89 w-m 32,29-31,70 2,77-2,82 m 35,60-35,02 2,52-2,56 w-m 36,50-35,45 2,46-2,53 w 42,40-41,58 2,13-2,17 w-m 43,69-42,61 2,07-2,12 w 49,21-48,65 1,85-1,87 w 50,98-49,79 1,79-1,83 w-m 55,30-54,23 1,66-1,69 w-m
    bei dem man eine Reaktionsmischung bildet, die reaktive Quellen von R, E, P, mindestens einem von M und Si enthält, und die Reaktionsmischung über einen zur Bildung des Metallophosphats ausreichenden Zeitraum auf eine Temperatur von 60°C bis 200°C erhitzt, wobei die Reaktionsmischung die folgende in Molverhältnissen der Oxide ausgedrückte Zusammensetzung aufweist: aR2O : bMO : E2O3 : cP2O5 : dSiO2 : eH2O wobei "a" einen Wert von 1 bis 16 hat, "b" einen Wert von 0 bis 2,0 hat, "c" einen Wert von 0,8 bis 8 hat, "d" einen Wert von 0 bis 4 hat und "e" einen Wert von 30 bis 800 hat.
  5. Metallophosphat nach Anspruch 1, modifiziert durch Ammoniak-Calcinierung unter Ammoniak-Calcinierungsbedingungen und gegebenenfalls einen zusätzlichen Ionenaustausch zur Bildung eines modifizierten mikroporösen Metallophosphats, AlPO-59M, mit einem dreidimensionalen Gerüst aus EO2 --Tetraedereinheiten, PO2 +-Tetraedereinheiten und mindestens einer von [M2+O2]2-- und SiO2-Tetraedereinheiten und der durch die folgende Summenformel gegebenen Zusammensetzung:

            M'n p+Mm 2+EPxSiyOz

    wobei M für mindestens ein Metallkation mit einer Wertigkeit von +2 aus der Gruppe bestehend aus Be2+, Mg2+, Zn2+, Co2+, Mn2+, Fe2+, Ni2+ steht, "m" für das Molverhältnis von M zu E steht und von 0 bis 1,0 variiert, M' aus der Gruppe bestehend aus NH4 +, H+, Alkalimetallen, Erdalkalimetallen Seltenerdmetallen und Mischungen davon ausgewählt ist, "n" für das Molverhältnis von M' zu E steht und einen Wert von 0,03 bis 2,0 hat, "p" für die gewichtete durchschnittliche Wertigkeit von M' steht, E für ein dreiwertiges Element aus der Gruppe bestehend aus Aluminium, Gallium, Eisen, Bor und Mischungen davon steht, "x" für das Molverhältnis von P zu E steht und von 0,5 bis 2,0 variiert, "y" für das Molverhältnis von Si zu E steht und von 0 bis 1, 0 variiert, "m" + "y" ≥ 0,1 und "z" für das Molverhältnis von O zu E steht und einen durch die folgende Gleichung bestimmten Wert aufweist: z = p • n + 2 • m + 3 + 5 • x + 4 • y / 2
    Figure imgb0015
     dadurch gekennzeichnet, dass es das Röntgenbeugungsmuster mit mindestens den folgenden d-Abständen und Intensitäten gemäß Tabelle A aufweist: Tabelle A 2Θ d (Å) I/I0 % 7,69-7,48 11,48-11,81 w 9,15-8,88 9,66-9,95 m-vs 12,55-12,25 7,05-7,22 m 13,30-13,07 6,65-6,77 w-s 14,90-14,51 5,94-6,10 w 16,13-15,87 5,49-5,58 m 16,75-16,37 5,29-5,41 w 18,28-18,02 4,85-4,92 m 19,94-19,41 4,45-4,57 w-m 20,88-20,64 4,25-4,30 m-vs 21,34-20,79 4,16-4,27 m 22,67-22,26 3,92-3,99 m-vs 23,08-22,78 3,85-3,90 w-s 25,28-24,78 3,52-3,59 w 26,11-25,43 3,41-3,50 s-vs 26,67-26,35 3,34-3,38 w-m 28,40-27,86 3,14-3,20 w 29,36-28,78 3,04-3,10 w-m 30,92-30,27 2,89-2,95 w-m 31,36-30,92 2,85-2,89 w-m 32,29-31,70 2,77-2,82 m 35,60-35,02 2,52-2,56 w-m 36,50-35,45 2,46-2,53 w 42,40-41,58 2,13-2,17 w-m 43,69-42,61 2,07-2,12 w 49,21-48,65 1,85-1,87 w 50,98-49,79 1,79-1,83 w-m 55,30-54,23 1,66-1,69 w-m
  6. Kristallines mikroporöses Metallophosphat nach Anspruch 1, AlPO-59, modifiziert durch Erhitzen des Metallophosphats nach Anspruch 1 unter Calcinierungsbedingungen zur Entfernung der organischen Kationen in Anwesenheit von Luft und Umgebungswasserdampf, wobei das AlPO-59C ein dreidimensionales Gerüst aus EO2 --Tetraedereinheiten, PO2 +-Tetraedereinheiten und mindestens einer von [M2+O2]2-- und SiO2-Tetraedereinheiten umfasst, gekennzeichnet durch die Summenformel:

            HaMm 2+EPxSiyOz

    wobei M für mindestens ein Metallkation mit einer Wertigkeit von +2 aus der Gruppe bestehend aus Be2+, Mg2+, Zn2+, Co2+, Mn2+, Fe2+, Ni2+ steht, "m" für das Molverhältnis von M zu E steht und von 0 bis 1,0 variiert, H für ein Proton steht, "a" für das Molverhältnis von H zu E steht und einen Wert von 0,1 bis 2,0 hat, E für ein dreiwertiges Element aus der Gruppe bestehend aus Aluminium, Gallium, Eisen, Bor und Mischungen davon steht, "x" für das Molverhältnis von P zu E steht und von 0,5 bis 2,0 variiert, "y" für das Molverhältnis von Si zu E steht und von 0,05 bis 1,0 variiert, "m" + "y" ≥ 0,1 und "z" für das Molverhältnis von O zu E steht und einen durch die folgende Gleichung bestimmten Wert aufweist: z = a + 2 • m + 3 + 5 • x + 4 • y / 2
    Figure imgb0016
     und dadurch gekennzeichnet, dass es das Röntgenbeugungsmuster mit mindestens den folgenden d-Abständen und Intensitäten gemäß Tabelle B aufweist: Tabelle B 2Θ d (Å) I/I0 % 9,42-9,02 9,38-9,80 m-s 12,95-12,49 6,83-7,08 m-s 13,68-13,20 6,47-6,70 vs 15,34-14,90 5,77-5,94 w-m 16,53-15,98 5,36-5,54 w-m 18,71-18,20 4,74-4,87 w-m 21,45-20,88 4,14-4,25 w-s 21,93-21,39 4,05-4,15 w-m 23,14-22,72 3,84-3,91 w-s 25,96-25,35 3,43-3,51 w-m 26,75-26,27 3,33-3,39 m-s 27,25-26,83 3,27-3,32 w-s 29,16-28,68 3,06-3,11 w-m 30,06-29,55 2,97-3,02 w-m 31,82-31,36 2,81-2,85 w-m 33,03-32,53 2,71-2,75 w-m
  7. Verfahren, bei dem man einen Kohlenwasserstoffstrom unter Kohlenwasserstoffumwandlungsbedigungen mit einem Katalysator in Berührung bringt, wobei man mindestens ein umgewandeltes Produkt erhält, oder bei dem man eine Wischung von mindestens zwei Komponenten mit einem Material in Berührung bringt, wobei man mindestens eine abgetrennte Komponente abtrennt, wobei der Katalysator bzw. das Material aus der Gruppe bestehend aus einem mikroporösen kristallinen AlPO-59-Material, einem mikroporösen kristallinen AlPO-59M-Material, einem mikroporösen kristallinen AlPO-59-C-Material oder Mischungen davon ausgewählt wird, wobei das AlPO-59 ein dreidimensionales Gerüst aus EO2 --Tetraedereinheiten, PO2 +-Tetraedereinheiten und mindestens einer von [M2+O2]2-- und SiO2-Tetraedereinheiten und eine durch die folgende Summenformel ausgedrückte empirische Zusammensetzung in der wie bei der Synthese anfallenden Form und auf wasserfreier Basis aufweist:

            RrMm 2+EPxSiyOz

    wobei M für mindestens ein Gerüstkation mit einer Wertigkeit von 2+ aus der Gruppe bestehend aus Erdalkali- und Übergangsmetallen steht, "m" für das Molverhältnis von M zu E steht und von 0 bis 1,0 variiert, R für das Organoammoniumkation Ethyltrimethylammonium (ETMA+) steht, "r" für das Molverhältnis von R zu E steht und einen Wert von 0,1 bis 2,0 hat, E für ein dreiwertiges Element aus der Gruppe bestehend aus Aluminium, Gallium, Eisen, Bor und Mischungen davon steht, "x" für das Molverhältnis von P zu E steht und von 0,5 bis 2,0 variiert, "y" für das Molverhältnis von Si zu E steht und von 0 bis 1,0 variiert, "m" + "y" ≥ 0, 1 und "z" für das Molverhältnis von O zu E steht und einen durch die folgende Gleichung bestimmten Wert aufweist: z = 2 • m + r + 3 + 5 • x + 4 • y / 2
    Figure imgb0017
     und dadurch gekennzeichnet ist, dass er das Röntgenbeugungsmuster mit mindestens den folgenden d-Abständen und Intensitäten gemäß Tabelle A aufweist: Tabelle A 2Θ d (Å) I/I0 % 7,69-7,48 11,48-11,81 w 9,15-8,88 9,66-9,95 m-vs 12,55-12,25 7,05-7,22 m 13,30-13,07 6,65-6,77 w-s 14,90-14,51 5,94-6,10 w 16,13-15,87 5,49-5,58 m 16,75-16,37 5,29-5,41 w 18,28-18,02 4,85-4,92 m 19,94-19,41 4,45-4,57 w-m 20,88-20,64 4,25-4,30 m-vs 21,34-20,79 4,16-4,27 m 22,67-22,26 3,92-3,99 m-vs 23,08-22,78 3,85-3,90 w-s 25,28-24,78 3,52-3,59 w 26,11-25,43 3,41-3,50 s-vs 26,67-26,35 3,34-3,38 w-m 28,40-27,86 3,14-3,20 w 29,36-28,78 3,04-3,10 w-m 30,92-30,27 2,89-2,95 w-m 31,36-30,92 2,85-2,89 w-m 32,29-31,70 2,77-2,82 m 35,60-35,02 2,52-2,56 w-m 36,50-35,45 2,46-2,53 w 42,40-41,58 2,13-2,17 w-m 43,69-42,61 2,07-2,12 w 49,21-48,65 1,85-1,87 w 50,98-49,79 1,79-1,83 w-m 55,30-54,23 1,66-1,69 w-m
    das mikroporöse kristalline AlPO-59M-Material ein dreidimensionales Gerüst aus EO2 --Tetraedereinheiten, PO2 +-Tetraedereinheiten und mindestens einer von [M2+O2]2-- und SiO2-Tetraedereinheiten und die durch die folgende Summenformel gegebene Zusammensetzung umfasst:

            M'n p+Mm 2+EPxSiyOz

    wobei M für mindestens ein Metallkation mit einer Wertigkeit von +2 aus der Gruppe bestehend aus Be2+, Mg2+, Zn2+, Co2+, Mn2+, Fe2+, Ni2+ steht, "m" für das Molverhältnis von M zu E steht und von 0 bis 1,0 variiert, M' aus der Gruppe bestehend aus NH4 +, H+, Alkalimetallen, Erdalkalimetallen, Seltenerdmetallen und Mischungen davon ausgewählt ist, "n" für das Molverhältnis von M' zu E steht und einen Wert von 0,03 bis 2,0 hat, "p" für die gewichtete durchschnittliche Wertigkeit von M' steht, E für ein dreiwertiges Element aus der Gruppe bestehend aus Aluminium, Gallium, Eisen, Bor und Mischungen davon steht, "x" für das Molverhältnis von P zu E steht und von 0,5 bis 2,0 variiert, "y" für das Molverhältnis von Si zu E steht und von 0 bis 1,0 variiert, "m" + "y" ≥ 0,1 und "z" für das Molverhältnis von O zu E steht und einen durch die folgende Gleichung bestimmten Wert aufweist: z = p • n + 2 • m + 3 + 5 • x + 4 • y / 2
    Figure imgb0018
     und dadurch gekennzeichnet ist, dass es das Röntgenbeugungsmuster mit mindestens den folgenden d-Abständen und Intensitäten gemäß Tabelle A aufweist: Tabelle A 2Θ d (Å) I/I0 % 7,69-7,48 11,48-11,81 w 9,15-8,88 9,66-9,95 m-vs 12,55-12,25 7,05-7,22 m 13,30-13,07 6,65-6,77 w-s 14,90-14,51 5,94-6,10 w 16,13-15,87 5,49-5,58 m 16,75-16,37 5,29-5,41 w 18,28-18,02 4,85-4,92 m 19,94-19,41 4,45-4,57 w-m 20,88-20,64 4,25-4,30 m-vs 21,34-20,79 4,16-4,27 m 22,67-22,26 3,92-3,99 m-vs 23,08-22,78 3,85-3,90 w-s 25,28-24,78 3,52-3,59 w 26,11-25,43 3,41-3,50 s-vs 26,67-26,35 3,34-3,38 w-m 28,40-27,86 3,14-3,20 w 29,36-28,78 3,04-3,10 w-m 30,92-30,27 2,89-2,95 w-m 31,36-30,29 2,85-2,89 w-m 32,29-31,70 2,77-2,82 m 35,60-35-02 2,52-2,56 w-m 36,50-35,45 2,46-2,53 w 42,40-41,58 2,13-2,17 w-m 43,69-42,61 2,07-2,12 w 49,21-48,65 1,85-1,87 w 50,98-49,79 1,79-1,83 w-m 55,30-54,23 1,66-1,69 w-m
    und das mikroporöse kristalline AlPO-59C-Material ein dreidimensionales Gerüst aus EO2 --Tetraedereinheiten, PO2 +-Tetraedereinheiten, SiO2-Tetraedereinheiten und gegebenenfalls [M2+O2] 2--Tetraedereinheiten umfasst, gekennzeichnet durch die Summenformel:

            HaMm 2+EPxSiyOz

    wobei M für mindestens ein Metallkation mit einer Wertigkeit von +2 aus der Gruppe bestehend aus Be2+, Mg2+, Zn2+, Co2+, Mn2+, Fe2+, Ni2+ steht, "m" für das Molverhältnis von M zu E steht und von 0 bis 1,0 variiert, H für ein Proton steht, "a" für das Molverhältnis von H zu E steht und einen Wert von 0,1 bis 2,0 hat, E für ein dreiwertiges Element aus der Gruppe bestehend aus Aluminium, Gallium, Eisen, Bor und Mischungen davon steht, "x" für das Molverhältnis von P zu E steht und von 0,5 bis 2,0 variiert, "y" für das Molverhältnis von Si zu E steht und von 0,05 bis 1,0 variiert, "m" + "y" ≥ 0,1 und "z" für das Molverhältnis von O zu E steht und einen durch die folgende Gleichung bestimmten Wert aufweist: z = a + 2 • m + 3 + 5 • x + 4 • y / 2
    Figure imgb0019
     und dadurch gekennzeichnet ist, dass es das Röntgenbeugungsmuster mit mindestens den folgenden d-Abständen und Intensitäten gemäß Tabelle B aufweist: Tabelle B 2Θ d (Å) I/I0 % 9,42-9,02 9.38-9.80 m-s 12,95-12,49 6,83-7,08 m-s 13,68-13,20 6,47-6,70 vs 15,34-14,90 5,77-5,94 w-m 16,53-15,98 5,36-5,54 w-m 18,71-18,20 4,74-4,87 w-m 21,45-20,88 4,14-4,25 w-s 21,93-21,39 4,05-4,15 w-m 23,14-22,72 3,84-3,91 w-s 25,96-25,35 3,43-3,51 w-m 26,75-26,27 3,33-3,39 m-s 27,25-26,83 3,27-3,32 w-s 29,16-28,68 3,06-3,11 w-m 30,06-29,55 2,97-3,02 w-m 31,82-31,36 2,81-2,85 w-m 33,03-32,53 2,71-2,75 w-m
  8. Verfahren nach Anspruch 7, bei dem das Kohlenwasserstoffumwandlungsverfahren aus der Gruppe bestehend aus Cracking, Hydrocracking, Alkylierung, Isomerisierung, Polymerisationen, Reformierung, Hydrierung, Dehydrierung, Umalkylierung, Dealkylierung, Hydratisierung, Dehydratisierung, Hydrotreating, Hydrofining, Hydrodenitrogenierung, Hydrodesulfurierung, Methanol-To-Olefins, Methanierung, Syngas-Shift-Verfahren, Olefindimerisation, Oligomerisation, Entparaffinierung und Kombinationen davon ausgewählt wird.
  9. Verfahren nach Anspruch 7, bei dem die Trennung auf der Molekülgröße der Komponenten, dem Polaritätsgrad der Komponenten oder dem Ionenaustausch der Komponenten mit dem Material basiert.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019023194A1 (en) * 2017-07-28 2019-01-31 Uop Llc CRYSTALLINE METALLOPHOSPHATES, PROCESS FOR THEIR PREPARATION AND USE
WO2019023313A1 (en) * 2017-07-28 2019-01-31 Uop Llc CRYSTALLINE METALLOPHOSPHATES, PREPARATION METHOD THEREOF AND USE THEREOF
US10493424B2 (en) 2017-07-28 2019-12-03 Uop Llc Crystalline metallophosphates, their method of preparation, and use
WO2019246338A1 (en) * 2018-06-22 2019-12-26 Uop Llc Crystalline metallophosphates, their method of preparation, and use
US10662069B2 (en) 2018-06-21 2020-05-26 Uop Llc Crystalline metallophosphates, their method of preparation, and use

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10421063B2 (en) * 2016-03-04 2019-09-24 Uop Llc High charge density silicometallophosphate molecular sieves SAPO-69
US10449528B2 (en) * 2016-03-04 2019-10-22 Uop Llc High charge density silicometallophosphate molecular sieves
WO2017205243A1 (en) * 2016-05-25 2017-11-30 Uop Llc High charge density metallophosphate molecular sieves
US10449526B2 (en) * 2016-05-25 2019-10-22 Uop Llc High charge density metallophosphate molecular sieves
WO2017204993A1 (en) * 2016-05-25 2017-11-30 Uop Llc High charge density metallophosphate molecular sieves
CN108472635B (zh) * 2016-05-25 2021-09-07 环球油品公司 高电荷密度金属铝磷硅酸盐分子筛MeAPSO-83
US10370257B2 (en) * 2016-05-25 2019-08-06 Uop Llc High charge density metalloaluminophosphosilicate molecular sieves
CN108473328B (zh) * 2016-05-25 2021-12-07 环球油品公司 高电荷密度金属磷酸盐分子筛
US10280089B1 (en) * 2018-06-22 2019-05-07 Uop Llc Crystalline metallophosphates, their method of preparation, and use
CN111099635B (zh) * 2018-10-25 2021-08-03 中国石油化工股份有限公司 Scm-19金属磷铝酸盐及其制备方法

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4319440A (en) 1979-10-11 1982-03-16 Rassias John N Building blocks, wall structures made therefrom and methods of making the same
US4440871A (en) 1982-07-26 1984-04-03 Union Carbide Corporation Crystalline silicoaluminophosphates
US4744970A (en) * 1984-04-13 1988-05-17 Union Carbide Corporation Cobalt-aluminum-phosphorus-silicon-oxide molecular sieves
US4973785A (en) 1984-04-13 1990-11-27 Uop Molecular sieve compositions
US4935216A (en) * 1984-04-13 1990-06-19 Uop Zinc-aluminum-phosphorus-silicon-oxide molecular sieve compositions
US4846956A (en) * 1984-04-13 1989-07-11 Uop Manganese-aluminum-phosphorus-silicon-oxide Molecular sieves
US4567039A (en) 1984-10-12 1986-01-28 Revlon, Inc. Hair conditioning composition and method
NO311208B1 (no) * 1996-03-13 2001-10-29 Norsk Hydro As Mikroporös krystallinsk metallofosfatforbindelse, en fremgangsmåte for fremstilling av forbindelsen og anvendelse derav
NO310106B1 (no) * 1996-03-13 2001-05-21 Norsk Hydro As Mikroporöse, krystallinske metallofosfatforbindelser, en fremgangsmåte for fremstilling og anvendelse derav
DK1142833T3 (da) * 2000-04-06 2010-04-19 Dalian Chemical Physics Inst Molekylære sigter
FR2837489B1 (fr) * 2002-03-20 2004-06-18 Inst Francais Du Petrole Solide cristallise im-6 de type metallophosphate et son procede de preparation
US6890511B2 (en) * 2003-03-21 2005-05-10 Uop Llc Crystalline aluminosilicate zeolitic composition: UZM-15
FR2854171B1 (fr) * 2003-04-24 2005-06-17 Inst Francais Du Petrole Solide cristallise im-8 de type metallophosphate et son procede de preparation
CA2539677C (en) * 2003-09-23 2012-08-28 Uop Llc Crystalline aluminosilicates: uzm-13, uzm-17, uzm-19 and uzm-25
WO2005113440A1 (en) * 2004-04-20 2005-12-01 Uop Llc Crystalline aluminosilicate zeolitic composition: uzm-15
CN102164856A (zh) * 2008-09-25 2011-08-24 环球油品公司 一种制备分子筛珠的方法
US8268290B2 (en) * 2009-08-04 2012-09-18 Uop Llc UZM-29 family of crystalline zeolitic compositions and a method of preparing the compositions
CN101993093B (zh) * 2009-08-25 2012-10-31 中国科学院大连化学物理研究所 一种具有rho骨架结构的sapo分子筛及其制备方法
ES2627947T3 (es) * 2012-06-29 2017-08-01 Uop Llc Tamices moleculares de metalofosfato, método de preparación y uso

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019023194A1 (en) * 2017-07-28 2019-01-31 Uop Llc CRYSTALLINE METALLOPHOSPHATES, PROCESS FOR THEIR PREPARATION AND USE
WO2019023313A1 (en) * 2017-07-28 2019-01-31 Uop Llc CRYSTALLINE METALLOPHOSPHATES, PREPARATION METHOD THEREOF AND USE THEREOF
US10493424B2 (en) 2017-07-28 2019-12-03 Uop Llc Crystalline metallophosphates, their method of preparation, and use
US10513440B2 (en) 2017-07-28 2019-12-24 Uop Llc Crystalline metallophosphates, their method of preparation, and use
US10570021B2 (en) 2017-07-28 2020-02-25 Uop Llc Crystalline metallophosphates, their method of preparation, and use
US10662069B2 (en) 2018-06-21 2020-05-26 Uop Llc Crystalline metallophosphates, their method of preparation, and use
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